Synthetic resinous material



' UNITED STATES PATENT a p k I 2, 214,'is9' Atlantic ReflningCompan 'Philadelphia, Pa, 'a corporationot lfennsylvani v No Drawing. Application 5,1937, SerialNo.,15'i,5 z8.

. v a mmc irr 1 The present invention relates to the production initial condensation products are shown in the of synthetic resinous products, and relates more following table: o, 7 Y particularly to resinous products obtained by the polymerization of condensation products of phos- Boilin point 1 phonitrilichalideswith organic compounds coni 1 Compound f tainingat least one reactive group. p 1a m./m. 70o m.[rn. Aprincipal object of this invention istheproduction of useful synthetic resinous products con- 0. tainlng phosphorous and nitrogen combined with i 5 28- 10 organic groups; Such products are usually hard, Polymer 1m: brittle, glassy solids, pale yellow to orange in is? g; color, stable to moisture and heat, insoluble in Depolyrnerims on distilwater, andrelatively insoluble invfatty oils, min- 1 eral oil, gasoline, benzene, ether, and other organic solvents. By varying the nature ot vthe Among the Organic QOmPOImdS w ch la a-Y organic groups in the initial condensation prod- D Y i P cing myinitial condensati ucts, and by varying the-conditions of time and p du tsjmaylbe me t e th hvdro y temperature in the polymerization treatment, a pounds such as methylalcohol and its homologues variety of resinous products may be obtained, ethyl, propyl, butyl, and amylalcohols; cresol;

ranging from very viscous liquids to plastics and xylenols; naphthols; benzyl alcohol; cyclohex- 50 hard, transparent solids. These resinous prodanol; furfuryl alcohol; hydroxy pyridine and the ucts may be suitably employed as ingredients in like. The mercaptan compounds maybe reprepaints, coatings, rubber, synthetic resins, andinsented by methyl mercaptan' and its homologues sulating compositions. as. resins adapted for ethyl, propyl, butyl, and 'amyl mercaptans; thiomoulding or shaping into a variety of articles; or phenol; thionaphthols;b enzyl mercaptanmyridyl I as agents which may begsuspended or colloldally mercaptans; and cyclohexyl mercaptan. The dispersedinlubrlcating oils or greases. v amino compounds'include methylamine and its My invention consists essentially in first prohomologues ethylamine, propylamlne, butylamine, ducing aninitialcondensationproduct of a phos- I amylamine; aniline; toludine; benzylamine;

phonitrilic halide with an organiccompound, and methylaniline; cyclohexylamlne; furflu'ylamine; a

, then subjecting such condensation product to piperidinaand other substitutedjarnmoniasconpolymerization by means of heat or other agency taining at least one reactive hydrogen atom,su'ch capable of producing a polymerizing action. The as phenylhydrazine. The halogenated hydrostep of thermal polymerization is preferably carbons may be represented by methyl chloride effected at a temperature of the order vof from and its homologues ethyl, propyl,=butyl and amyl I about 200? C. to about v 100 C. and under sub-atchlorides; chloroor bromobenzene and their mos'pheric, atmospheric or superatmospheric homologues'; chloro-cyclohexanm'and the chloropressure. Or, I may carryout the polymeriza- 'naphthalenes. Other' halogenated compo nds tion in the presence of an inert gas such as carwhich may be suitably employed include the halo- 40 bon dioxide, nitrogen or the like. As a result of genated furanes; halogenated pyridine; halog ho the polymerization, the initial condensation prodated quinoline; 1 and the various halogenated a1- uct is converted into a high molecular weight rescohols, phenols, mercaptans, amines and the like. inous material. I I I I The condensation reactions for, producing the The syntheticresinous products which may be initial condensation products, when employing, produced in accordance with my invention are for example (PNCl2)s.and a-hydro'xy compound, a 45 those resulting from the polymerization of the mercaptan, and an amine, respectively, may be condensation products of the phosphonitrilic represented by the following equations: halides, and particularlyv the phosphonitrilic chlorides,with aliphatic,aromatic,hydroaromatic,

or heterocyclic alcohols, mercaptans amines' and I v o halogenated hydrocarbons, or other compounds 5 .(PNC12)3+6RTNH2 [(RNH) 2?N3+6HC1, containingofunctions capable of reaction or con- In the above reaction R may be either an densation with the phosphonitrilic halides. aliphatic, hydroaromatic, aromatic, or hetero- The phosphonitrilic halides, and particularly cyclic radical. Furthermore, the reactions may as the chlorides, which I employ in producing my be carried on in the presence or absence of cataamine and the mixture was refluxed at about C. for about 5 hours. After refluxing was lysts, and it is not always necessary to employ sufficient of the hydroxy, mercaptan, amino or halogenated hydrocarbon compound to react completely with the phosphonitrilic halide, since in some instances it may be desirable to retain a certain amount of the halogen in the condensation product. Among the catalysts which may be employed may be mentioned copper oxide, copper sulfate, magnesium oxide and magnesium chloride. g

In accordance with my invention, two general methods of preparing the initial condensation products may be employed. The first is the relatively low temperature, for example, less than 150 C. and preferably about 0., reaction of the phosphonitrilic halide with. a metallic salt of the organic compound which it is desired to condense therewith. This reaction is preferably carried out in the presence of an inert solvent or suspension medium. The second method involves the heating of the phosphonitrilic halide with the desired organic compound in a vessel provided with a reflux condenser. The latter method is particularly applicable to the condensation of the phosphonitrilic halide with phenols or thiophenols, since it is characteristic of them that the side reactions which may occur with the alcohols or mercaptans do not take place to an appreciable extent. Thus, higher temperatures may be employed which permit a faster reaction rate. In the case of the alcohols and aliphatic mercaptans, it is desirable to operate at a lower temperature, and, in order to increase the rate of reaction, the alcohol or mercaptan is first caused to combine with-a metal, for example, sodium or potassium, to produce an alcoholate or'mercaptide which is considerably more reactive than the alcohol or mercaptan from which it is derived. In either of the aforementioned procedures, it may be desirable to carry out the condensation reaction under superatmospheric pressure, for example, of the order of 100 lbs./sq. in., or greater, in. order to accelerate the rate of reaction. The condensation of mercaptans or thiophenols with the phosphonitrilic halide is preferably effected in an inert atmosphere to prevent excessive oxidation of the reactants. Methane, nitrogen, or other inert gas may be employed for this purpose.

The initial condensation product of the phosphonitrilic halide with an organic compound, which may be produced'as above described, is subjected to a. polymerizing action, such as heating to temperatures of the order of from about 200 C. to about 400. 0., whereby the initial condensation product is converted to a polymerized resinous product. Temperatures lower than about 200 C. may be employed provided the duration of the heating step is sumcient to effect the de-' sired polymerization. The polymerization may.

also be effected by subjecting the initial condensation product to the action of ultrasonic waves, or, light of suitable wave length, or to the action of catalytic agents such as AlCla, Z11C12,BF3 and the p v I Y Y tially insoluble'in organic solvents, comprising a p0ly'merized condensation product of a phosphonitrilicchloride with a lower aliphatic amine like.

A typical example of my product and preparing the same is as follows:

5.8 parts by weight of phosphonitrilic chloride,

comprising substantially (PNC12)3' and (PNCh) 4, was dissolved in anhydrous benzene. To this solution was added 16.4 parts by weight of 'n-butylcompleted, the reaction product was filtered and the filtrate was distilled under reduced pressure glassy solid which was stable to heat, insoluble in water and organic solvents, and resistant to the action of acids and alkalis.

It will be seen from the above example, that .there may be produced a resinous material by condensing a phosphonitrilic halide with an organic compound containing at least onereactive group, for example, an amino compound, followed by the polymerization of the condensation product., In lieu of the amino compound there may be employed alcohols, phenols, mercaptans and the like. Any organic compound containing an active group or replaceable hydrogen atom'may be employed in my condensation reaction.

In the formula for the condensation product of the above example, subscript "11 usually ranges from 3 to 7, depending upon the phosphonitrilic halideemployed and the "temperature required to effect the initial condensation. When the-phosphonitrilic halide comprises essentially (PNC1z)3 or (PNC12)4, and the reaction temperatures are" soluble in organic solvents from a condensation product of a phosphonitrilic chloride with butylamine, the step which comprises heating said condensation product to a temperature within the range of from about 200 (Ito about 400 C.,

under substantially reduced pressure, to veiifect polymerization thereof.

2. Ina process for producing a light colored,

solid synthetic resinous material substantiallyin-i I soluble in organic solvents from a condensationproduct of a phosphonitrilic chloride with a lower aliphatic amine containing'atleast one hydrogen atom bonded to the nitrogen atom, the step'which comprises heatingsaid condensation product to a .temperature within the range of" from about "-200" C. to about 400- C.'"under substantiallyreduced pressureto eifect polymerization thereofi- '3. I A light colored, solid synthetic resin substanpolymerized condensation product of a phosphonitrilic chloride with n-butylamine.

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